Abstract
In a way similar to previous calculations by other authors of molecular photoionization cross sections, theoretical expressions for atomic X-ray photoionization cross sections are derived using Slater-type orbitals and the plane wave approximation. Relative results for 1s cores of first-row atoms are close to experiment. Calculated 2s/2p ratios greatly disagree with empirical and semi-empirical data obtained from X-ray photoelectron spectra (XPS) unless orthogonalized 2s orbitals are used. In the latter case, fair agreement is obtained. Finally, a new viewpoint for correlating relative XPS or ESCA line intensities with s/p character is outlined for molecules consisting of first-row atoms.
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